DE4016564A1 - RESIN COMPOSITIONS FOR ELECTROPHOTOGRAPHIC TONERS - Google Patents

Description

The invention relates to toner compositions suitable for toner compositions and in particular those which are known as binders tel are suitable for electrophotographic toner.

In electrophotography (xerography) are methods the one heated roller for fixing electrostatically use latent images, which with the help of a Evolution Toner's are made visible, far common. With these procedures is a low Minimum temperature for fixing (hereinafter referred to as MF designated) and a high temperature for detachment from the heated roll (hereinafter referred to as HO) he wishes. In an effort to meet these two requirements are previously different toner binders with a broad molecular weight distribution of a lower to a higher molecular weight has been proposed (Japanese Patent Publ Nos. 20 411/1985 and 23 354/1976). A disadvantage of this method is that the Verwen use of crosslinking agents to obtain higher Molecular weights leads to a higher MF and that it difficult without the use of crosslinking agents is the required higher molecular weight and to achieve a sufficient HO.

Accordingly, the invention is based on the object a resin composition having a broad molecular weight to provide weight distribution.  

It is also an object of the invention to provide a toner to provide a suitable binder, a Toner with the desired properties of a low MF and a high HO.

It is another object of the invention to provide a manufacturer method for a resin composition having a broad molecular weight distribution and a method for fixing a toner image to provide is suitable for low MF and high HO guarantee.

These tasks are done by a for electrophotogra dissolved in a phobic toner suitable resin composition, which is a high molecular weight copolymer (A) with a mole of at least 3 00 000 by Copoly merisation of (a) at least one styrenic monomer and (b) at least one acrylic or methacrylic monomer without or with (c) at least one other monomer in the presence of at least one polyfunctional Polymerization was obtained.

Suitable polyfunk used in this invention Normal polymerization initiators include those with at least two peroxide groups and those with at least one peroxide and at least one poly merisable unsaturated group.

Polyfunctional polymerization initiators with min at least two peroxide groups include, for example those represented by the general formula (1)

be reproduced.  

In formula (1), R is an alkyl group containing 1 to 8 carbon atoms, m is an integer of 2 - 4, p is 0 or 1, and A is a polyvalent organic group containing at least 4 carbon atoms. Among the alkyl groups (R) tert-butyl are preferred. Examples of this polyvalent organic group are aliphatic hydrocarbon groups (including alkylene, alkenylene and alkynylene groups) which usually contain 2 to 10, preferably 4 to 8, carbon atoms, such as butylene, trimethylbutylene, hexylene, dimethylhexylene, octylene and dimethyl hexynylene groups, cycloaliphatic hydrocarbon groups usually containing 6 to 20, preferably 6 to 15 carbon atoms, such as cyclohexylene and trimethylcyclohexylene groups and

Aromatic hydrocarbon groups usually containing 6 to 20, preferably 6 to 15 carbon atoms, such as -C ₃ H ₆ -phenylene-C ₃ H ₆ -, heterocyclic groups, such as a triazine ring and aliphatic hydrocarbon groups, usually 4 to 20, preferably, as 6 to 15 carbon atoms and one or more functions selected from the ester and ether compounds, such as C ₂ -C ₈ alkylene groups substituted by -COOR 'or -OR' (R ': C ₁ -C ₈ alkyl group) included. Examples of polyfunctional polymerization initiators having at least two peroxide groups are 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 1,3-bis (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-2, 5-di- (tertiarybutylperoxy) -hexane, 2,5-dimethyl-2,5-di- (tertiarybutylperoxy) -3-hexyne, tris (tertiarybutylperoxy) triazine, 1,1-di tert-butyl peroxycyclohexane, 2,2-di- (tert-butylperoxy) butane, 4,4-di-tert-butylperoxyvaleric acid n-butyl ester, di-tert-butylperoxyhexahydroterephthalate, di-tert. butylperoxyazelate, di-tert-butylperoxytrimethyl adipate, 2,2-bis (4,4-di-tert-butylperoxycyclohexyl) propane, 2,2-di-tert-butylperoxyoctane and polymer peroxides. These include 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, di-tert-butylperoxyazelate and 2,2-bis (4,4-bis) Di-tert-butyl peroxycyclohexyl) propane.

Polyfunctional polymerization initiators with min at least one peroxide group and at least one poly merizable unsaturated group include, for example include those represented by the general formula (2)

R₁-OO-CO- (O) _p (CH₂) _n -CH = CH-R₂ (2)

be designated. In formula (2), R _{1 is} an alkyl group containing 1 to 8 carbon atoms or R₂-CH = CH- (CH₂) _n (O) _p -CO-, p is 0 or 1, n is an integer of 0-8 , R _{2 is} hydrogen, -COOH or -COOR 'and R' is an alkyl group containing 1 to 8 carbon atoms.

Examples of these alkyl groups R ₁ and R 'are isopropyl and tert-butyl groups. Examples of polyfunctional polymerization initiators having at least one peroxide group and at least one polymerizable unsaturated group include diallyl peroxycarbonate, tert-butyl peroxymaleic acid, tert-butyl peroxyallyl carbonate and tert-butyl peroxyisopropyl fumarate. Of these, tert-butyl peroxyallyl carbonate is particularly preferred.

Suitable styrenic monomers (a) are those of the formula (3)

In formula (3), R ₃ , R ₄ and R _{5 are} independently selected from the group formed by hydrogen and lower alkyl, R _{6 is} that of hydrogen, C ₁ -C ₁₀ alkyl, phenyl, lower alkoxy and halogen Ar is an aromatic hydrocarbon group (such as phenylene) and q is an integer of 0-3.

Examples of such monomers (a) are styrene, styrene homologous or substituted styrenes, including alkyl (C ₁ -C ₈ ) styrenes such as alpha-methylstyrene, o-, m and p-methylstyrenes, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, aryl-substituted styrenes such as p-phenylstyrene, alkoxy-substituted styrenes such as p-methoxy-styrene, halosubstituted styrenes such as p-chlorostyrene and 3,4-dichlorostyrene and mixtures of two or more of them, such as mixtures of styrene with one or more styrene homologs. Styrene is particularly preferred.

The suitable acrylic or methacrylic monomer ( b ) to summarizes esters of (meth) acrylic acids (acrylic acid and methacrylic acid, corresponding names are used hereinafter), for example alkyl (C ₁ - C ₁₈ ) (meth) acrylates, such as methyl, ethyl , n- and i-butyl, propyl, n-octyl, 2-ethylhexyl, dodecyl, lauryl and stearyl (meth) acrylates, aryl (meth) acrylates, such as phenyl (meth) acrylates, hydroxyl-containing (meth ) acrylates such as hydroxyethyl (meth) acrylates, amine-containing (meth) acrylates such as dimethylaminoethyl and diethylaminoethyl (meth) acrylates, epoxy-containing (meth) acrylates such as glycidyl (meth) acrylates, (meth) acrylic acids and their derivatives, such as (Meth ) acrylonitriles and (meth) acrylamides. Of these, alkyl (meth) acrylates (in particular methyl, ethyl, butyl and 2-ethylhexyl (meth) acrylates) and (meth) acrylic acids and mixtures of two or more of them are preferred.

Suitable further monomers ( c ), which are optionally used for the preparation of high molecular weight copolymers in the prior invention include, for example, vinyl esters such as vinyl acetate and vinyl propionate, aliphatic hydrocarbon monomers such as butadiene, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methylisopropenyl ketone, N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidine. Of these, the vinyl esters and aliphatic hydrocarbon monomers are preferred.

In addition to these monomers (a), (b) and gege if appropriate (c) can also be at least one poly functional, at least two polymerizable Double bond-containing monomer (d) in Rah men of this invention in a proportion that no Gelling causes be used. examples for the monomers (d) are di- or polyvinyl compounds, for example, aromatic di- or polyvinyl compound such as divinylbenzene and divinyltoluene and di or poly (meth) acrylates of the polyols, such as ethylene glycol di (meth) acrylates, 1,6-hexanediol di (meth) acrylates. Of these are divinylbenzene and 1,6-hexane diol diacrylate is preferred.

For the preparation of the high molecular weight according to the invention The copolymers can contain the contents of the monomers (a), (b), (c) and (d) vary within wide limits, however, the usual, on the total content of Monomer-related ranges as follows:

The high molecular weight copolymer (A) can be replaced by Copoly merization of the monomers (a) and (b) with or without the monomers (c) and / or (d) in the presence of min at least one polyfunctional polymerizationini tiator be prepared by one of be knew polymerization processes such as solvent, Bulk, suspension and emulsion polymerization as well as their combinations (as solution followed by Suspension or bulk polymerization or suspension ion-followed by solvent or bulk poly merisation) uses.

The content of the polyfunctional polymerization initiators can vary within wide limits, be However, in general, 0.02-1.0%, preferably Example 0.03 - 0.8%, based on the total weight the monomers.

Solvent suitable for solvent polymerization for example, cycloalkanes such as Cyclohexane, aromatic hydrocarbons such as benzene, Toluene, xylene, ethylbenzene and cumene, esters such as Ethyl acetate and butyl acetate and ethers, such as methyl cellosolve, ethylcellosolve and butylcellosolve. Of these, the cycloalkanes and aromatic carbons hydrogens to obtain higher molecular weight polymers prefers.

The suspension polymerization can be carried out in aqueous Medium in the presence of dispersants at For example, inorganic such as calcium carbonate and Calcium phosphate and organic such as polyvinyl alcohol hol and methylcellulose.  

The polymerization temperature is usually 50 ° C to 150 ° C or more, preferably 60 ° C to 120 ° C. In the last polymerization stage (at For example, after the degree of conversion reaches 60% the temperature can be at 150 ° C to 200 ° C or be increased more.

Preferably, the polymerization is in one Inertgasatmosphäre example, under stick fabric carried out.

The polymerization of the monomers can be simultaneous or stepwise, i. on Part of the monomers is polymerized, followed from the polymerization of the monomer residue in Mi Schung with the resulting polymer.

The molecular weight of high molecular weight, under Use of polyfunctional polymerization Ticators obtained according to the invention (A) can vary within wide limits, but are such with an average molecular weight (Mw) passing through GPC (gel permeation chromatography) using Tetra hydrofuran (hereinafter referred to as THF) under Using a calibration curve of the standard poly styrene can be measured from at least about 300,000, preferably from about 350,000 to about 3 000 000 or higher, in particular around 400 000 to about 2,000,000.

Resin compositions for toner according to the invention Binders include the high molecular weight copolymer (A) and may continue to have one or more others Contain ingredients.  

With regard to the reduction of MF it is preferred that one or more low molecular weight Components are included.

Preferred examples of such ingredients include at least one further polymer (B) with low rem molecular weight, for example polymers with an Mw of usually about 3,000 to about 50,000, such as styrene / acrylic copolymers, polyester, polyepoxide and Polyurethane resins. Of these are styrene / acrylic copolymers and polyester resins are preferred.

In preferred embodiments, the further Polymers (B) previously, separately or together with the high molecular weight polymers are produced. With In other words, the toner binder resin compositions by mixing in a solution or in the molten state of (A) with (B), before prepared separately or by copolymerization of Monomers (a) and (b) in the presence of (B) and the polyfunctional polymerization initiator produced become. These methods of previous manufacture of (B), separately or together with (A) Resin compositions provide (A) with enough high Mw, without reducing Mw of (A).

In another embodiment, the other Polymers (B) by bulk or solvent polymers sation of at least one precursor monomer for (B) are prepared in the presence of (A). at For example, (A) in this precursor monomer dissolved and then this precursor monomers to obtain (B) polymerized. For the poly  merisation of this precursor monomer can in in this case, bulk and solvent polymerization which contains the content of Polymerisa tioninitiator to provide the same Moleku considerable weight and therefore harmful Liche influences (such as exceptional charging of the toner, instability to environmental influences etc.) caused by the presence of initiator residues caused, avoided or reduced can and is therefore preferred.

In these resin compositions, the other Polymers (B) and the High Molecular Weight Copolymer (A) mixed only or chemically as by ko tie valent bond. In this Harzzu The content of (A) is usually 10 to 50 wt.%, Preferably 15 to 45 wt.% And the of (B) is generally 50% by weight to 90% by weight, preferably 55% by weight to 80% by weight, based on the Total weight of these polymers.

Mw of the toner binder resin composition of the present invention Compositions is usually about 100,000 to about 2,000,000, preferably about 150,000 to about 1,500,000. If Mw is less than 100,000, it is difficult to to achieve a sufficient HO and at Mw greater than 2 000 000, the MF is too high. The molecular weight distribution (represented by the ratio of Mw to the average molar weight number (Mn), i. Mw / Mn) of the toner binder resin according to the invention Compositions is generally at least about 20, preferably at least about 30 Mw / Mn of less than 20 gives a bad balance  between HO and MF. The glass transition temperature Tg of the inventive toner binder resin Compositions is generally about 40 to about 80 ° C, preferably about 45 to about 70 ° C. resin give compositions with Tg of less than 40 ° C Toner with poor storage stability and if Tg is greater than 80 ° C, MF becomes too high to be practical to be used for toner.

The toner binder resin composition of the present invention Compositions may be at least one low molecular weight Polyolefin (C) included. The Mw of this polyolefin (C), which by GPC using o-dichloro benzene can be measured at 135 ° C, is in General about 1000 to about 100 000, preferably about 5,000 to about 60,000. Examples of this Polyolefins (C) are:

(C1) polyolefins, for example polyethylene, polypropylene and copolymers of ethylene with an alpha-olefin containing 3-8 carbon atoms, such as ethylene-propylene copolymer, which contains at least 50%, in particular at least 70% by weight of propylene,
(C2) (C1) modified with (adducts of (C1) with) maleic acid derivative (such as maleic anhydride, dimethyl maleate, diethyl maleate and 2-diethyl hexylmaleate),
(C3) oxidation products of (C1),
(C4) copolymers of alkenes such as ethylene, propylene, 1-butene with alkenylcarboxylic acid such as (meth) acrylic acids, itaconic acid and / or their esters such as C ₁ to C ₁₈ alkyl esters,
and mixtures of two or more thereof.

Among the above polyolefins (C), (C1) may be replaced by ther mix degradation (thermal decomposition) of higher molecular polyolefins (Mw usually about 10,000 to about 2,000,000) or by polymerization of a or more olefins. (C2) can by addition reaction of maleic acid derivatives with (C1), in the presence of or without peroxide catalyst be obtained. (C2) can be due to oxidation of (C1) containing oxygen or oxygen Gas (such as air) or ozone-containing oxygen or ozone-containing gas (air). The acid value of (C2) is usually at most about 100, preferably at most about 50. (C4) by copolymerization of olefin with alkenylcarbon acid and / or its ester. The salary Alkenylcarboxylic acid and / or its ester is in the generally at most about 30%, preferably max at least about 20%.

It is preferred that the polyolefin (C) be homogeneous in the resin composition to achieve distributed release effects is distributed.

For this purpose, (C) is preferably used during the Polymerization of the monomers (a) and (b) added.

The content of the polyolefin (C) is usually at most about 30%, preferably about 1 to about 20%, based on the total weight of the toner bandage means. The use of (C) with more than 30% leads to an insufficient dispersibility.  

The electrophotographic toner in which the inventions The resin composition of the present invention as a toner binder generally comprises about 50% by weight to about 95% by weight of the toner binder and may be one or more known dyes, for example inorganic and organic pigments such as carbon black, iron black, benzidine yellow, quinacridone pigments, rhodamine B and phthalocyanine pigments containing usually about 5 to about 10%, magnetic powders like powders of ferromagnetic metals and compounds, like iron, cobalt, nickel, magnetite, hematite and Ferrite, containing in general from 0 to about 50% and other additives such as charge reg Such as metal complexes and nigrosine, lubricants such as polytetrafluoroethylene, low molecular weight polyols fine, fatty acids and their metal salts or theirs Amides, containing from 0 to about 5%.

The toner can be made by dry blending this stock followed by melting with kneading coarse grinding and subsequent fine pulverization with a mill (like a jet mill) and Classifi coating to particles of 50 - 20 microns to be obtained.

The toner may optionally contain one or more Carrier particles such as iron powder, glass beads, nickel mixed powder and ferrite and as a developer for electrically latent images are used. additionally For example, colloidal hydrophobic silica powder may be used for Improved the castability of the powder used become.  

The toner can be applied to substrates such as papers and polyesters be bound. This bond can be with any be knew about binding methods like fixation by a heated roll to be performed.

In the following examples, parts mean ratios and percentages, parts by weight, weight ratios and Weight.

The measurement conditions for Mw by GPC are as follows:

Device: HCL-802A manufactured by Toyo Soda Manuf. Columns: TSK Gel GMH6, 2 columns, manufactured by Toyo Soda Manuf. Temperature: 25 ° C Sample solution: 0.5%, THF solution Solution content: 200 microliters Detector: refractometer

The Mw calibration curve was calculated using Standard polystyrenes produced.

example 1

In a 1 liter four-necked flask, 450 parts of water and 50 parts of a 2% aqueous solution of poly vinyl alcohol (PVA 235, manufactured by Kuraray), then a mixture of 250 parts of styrene, 83 Parts of n-butyl acrylate and 1 part of 1,1-di-tert-butyl peroxy-3,3,5-trimethylcyclohexane to form a Suspension added with stirring. After the off exchange of the piston atmosphere with nitrogen the temperature to 80 ° C to initiate the Polymeri increased. The polymerization was at the same  Temperature continued and after finding that the conversion reached 98% after 20 hours, the temperature was raised to 95 ° C, afterwards This was followed by the suspension polymerization according to FIG Hours completely. The resulting polymer was removed filtered, washed with water and dried for Obtaining a polymer (hereinafter referred to as polymer A-1 with a Mw of 1 200 000 and Tg of 60 ° C.

Meanwhile, 300 parts of xylene in a 2 liter Four-necked flask filled and then drerei after nitrogen, the temperature was at the boiling point of xylene increased (about 140 ° C) for the reflux. This was under Xylene reflux a mixture of 500 parts of styrene, 120 parts of methyl methacrylate, 47 parts of butyl acrylate and 47 parts of tert-butyl peroxybenzoate for 4 hours added dropwise and the xylene reflux another 2 hours for complete polymerization continued. The resulting solution is subsequently referred to as solution A-2.

To solution A-2 was added 333 parts of Polymer A-1 added and dissolved under xylene reflux, then by distilling off the xylene an inventive Binders obtained (hereinafter referred to as Binder A-3).

The binder A-3 contained 32% of a high molecular weight Copolymers having a molecular weight of at least 300 000 and had a Mw of 250 000 and a Tg of 63 ° C as determined by GPC and Tg measurements.  

Example 2

Xylene was from solution A-2 of Example 1 for recovery a polymer (hereinafter referred to as polymer B-2 net) distilled off. A mixture of 365 parts styrene, 135 parts of 2-ethylhexyl acrylate and 1.2 parts of Di-tert-butylperoxyhexahydroterephthalate became 500 Divide the polymer B-2 to obtain a homogeneous Solution added. This solution was at 80 ° C in a glass autoclave in the same way as for Production of the polymer A-1 in Example 1 suspen sionspolymerisiert. When the conversion reached 90%, the temperature was raised to 120 ° C, then the complete suspension polymerization took place within 3 hours.

The resulting polymer was filtered off, with water washed and then in the same way as in Example 1 for obtaining a bandage according to the invention by (hereinafter referred to as binder B-3) dried.

Binder B-3 contained 45% of a high molecular weight laren copolymers with a molecular weight of min at least 300 000 and had a Mw of 300 000 and a Tg of 64 ° C, which was measured by GPC and Tg was determined.

Example 3

In the same way as in the production of Lö Solution A-2 of Example 1, styrene was obtained polymerized a polymer solution, then the Xylene for obtaining a polymer (hereinafter referred to as  Polymer C-2) distilled off. A mixture from 216 parts of styrene, 84 parts of n-butyl acrylate and 0.5 part of 2,2-bis (4,4-t-butylperoxycyclo hexyl) propane was added to 300 parts of Polymer C-2 for the preparation of a homogeneous solution. This solution was made into a corrosion resistant Pressure reaction vessel of 2 l content and after sufficient nitrogen atmosphere at 80 ° C poly merized. When the conversion reached 60%, the temperature was increased to 190 ° C and 360 parts Styrene and 40 parts of n-butyl acrylate dropwise in the reaction vessel is added for 2 hours, subsequently, the polymerization became for 1 hour continued and the unused monomers to Obtaining a binder according to the invention (hereinafter referred to as binder C-3) from distilled.

The binder C-3 contained 21% of a high mol gular copolymers having a molecular weight of at least 300 000 and had a Mw of 280 000 and a Tg of 58 ° C, which was measured by GPC and the Tg was determined.

Example 4

In a corrosion-resistant pressure reaction vessel with 2 liters of content were 360 parts of styrene, 150 parts of n-butyl acrylate and 0.25 parts of 2,2-bis (4,4-tert-butylperoxy) cyclohexylpropane filled, then after drerei nitrogen atmosphere Polymerized 110 ° C. When the conversion reaches 65% 100 parts of xylene were added and the Temperature increased to 205 ° C for 2 hours. At the  This temperature was 450 parts of styrene and 50 parts n-butyl acrylate dropwise into the reaction vessel Added for 6 hours, then the poly continued for 2 hours and not consumed monomers and xylene under reduced pressure to Obtaining a binder according to the invention (according to hereinafter referred to as binder D-3) distilled off.

The binder D-3 contained 26% of a high molecular weight laren copolymers having a molecular weight of at least 300 000 and had a Mw of 250 000 and a Tg of 60 ° C, which by measuring with GPC and the Tg was determined.

Comparative Example 1

Example 1 was repeated with the change that Benzoyl peroxide as a monofunctional polymerization initiator instead of the difunctional polymerization initiators 1,1-di-tert-butylperoxy-3,3,5-trimethyl cyclohexane for the preparation of the polymer A-1 of the Bei game 1 for obtaining a binder (hereafter as binder E-3) was used.

Binder E-3 contained only 5% of a high molecular weight Copolymers having a molecular weight of at least 300,000 and had a Mw of 20,000 and a Tg of 65 ° C, which is determined by measuring with GPC and Tg has been.  

Examples I-V

88 parts of each of the binders of the invention Examples 1 to 4 and the binder of the comparison Example 1 were homogeneously mixed with 7 parts of carbon black (MA 100, manufactured by Mitsubisi Chemical Industries), 3 parts of a low molecular weight polypropylene (Vis col 550 P, manufactured by Sanyo Chemical Industries) and 2 parts of a charge controller (Spironblack TRH, manufactured by Hodogaya Chemical Co.) and then by means of a twin-screw extruder with kneaded at a melt temperature of 150 ° C, then The cooled kneaded mixture became one Jet mill finely pulverized and then with a Dispersion separator for the recovery of toners with an average of 12 microns in diameter fied.

3 parts of each toner became homogeneous with 97 parts a ferrite carrier (EFV 200/300, manufactured by Nippon Seihun Co.) and the fixations Testing using a commercial electro Photographic copier (BD-7720, manufactured by Toshiba Corp.).

The test results are shown in Table 1.

Table 1

As shown in Table 1, those using the inventive binders A-3, B-3, C-3 and D-3 obtained toner I, II, III and IV a size temperature range between MF and HO and a higher desired thermal performance than Toner on, like the one using the binder E-3 Toner for Comparative Purification V.

Resin compositions according to the invention have a broad molecular weight distribution and are as Binder for electrophotographic toner containing desirable properties with respect to MF and HO (low MF and high HO), effectively.

Claims (16)

1. An electrophotographic toner suitable resin composition comprising a high molecular weight Copoly meres having a molecular weight of at least 300,000, obtainable by copolymerization (a) of at least one aromatic Vinylmono meren with (b) at least one α- methylene aliphatic Monocarbonsäureestermonomeren and optionally (c ) at least one other monomer, in the presence of at least one polyfunctional polymerization initiator selected from the group consisting of a polymerization initiator having at least two peroxide groups and a polymerization initiator having at least one peroxide group and at least one polymerizable unsaturated group. 2. Composition according to claim 1, characterized in that the initiator is selected from the group consisting of

• 1) a compound of the general formula wherein R is an alkyl group containing 1-8 carbon atoms, m is an integer of 2-4, p is 0 or 1, and A is an organic group containing at least 4 carbon atoms selected from aliphatic hydrocarbon, cycloaliphatic hydrocarbon, aromatic carbons hydrogen, heterocyclic and aliphatic hydrocarbon groups containing one or more ester and / or ether compounds, and 2) a compound of the general formula R₁-OO-CO- (O) _p (CH₂) _n -CH = CH-R₂ (2) wherein R _{1 is} an alkyl group containing 1 to 8 carbon atoms or R₂-CH = CH- (CH₂) _n (O) _P -CO- p o or 1, n is an integer from 0 to 8, R _{2 is} H, -COOH or -COOR 'and R' is an alkyl group containing 1 to 8 carbon atoms.

3. Composition according to claim 1 or 2, characterized characterized in that the high molecular weight copolymer at least 50% by weight of the monomer (a) units, 2 to 50% by weight of the monomer (b) units and 0 to 10% by weight of the monomer (c) units ent holds. 4. Composition according to one of claims 1 to 3, characterized in that it contains 10 to 50% by weight of the high molecular weight polymer and 50 to 90% by weight at least one further polymer with lower Includes molecular weight. 5. Composition according to claim 4, characterized characterized in that the further polymers with lower Molecular weight previously separated from or common sam made with the high molecular weight polymer is.   6. Composition according to claim 4 or 5, characterized characterized in that the further polymer with lower molecular weight by mass or Solvent polymerization is prepared. 7. Composition according to one of claims 1 to 6, characterized in that it is a medium mole from about 100,000 to about 2,000,000 having. 8. Composition according to one of claims 1 to 7, characterized in that it has a glass transition temperature of about 40 ° C to about 80 ° C. 9. Composition according to one of claims 1 to 8, characterized in that they additionally min at least one low molecular weight polyolefin and / or Dye and optionally a magnetic Powder and / or one or more other additives contains. 10. Process for the preparation of a composition according to one of claims 4 to 6, characterized records that it is the copolymerization of the mono meren (a) and (b) in the presence of the other Polymers and polyfunctional polymers tioninitiators includes. 11. Process for the preparation of a composition according to one of claims 4 to 6, which the Copoly merization of the monomers (a) and (b) in Gegen the polyfunctional polymerization tiators and mixing the resulting high molecule laren copolymers with the other polymers to summarizes.   12. Process for the preparation of a composition according to one of claims 4 to 6, characterized ge indicates that it is the copolymerization of Monomers (a) and (b) in the presence of poly functional polymerization initiator and Polymerization in bulk or in the solvent of at least one precursor monomer of the white teren polymers in the presence of the resulting high molecular weight copolymers. 13. Process for the preparation of a composition according to claim 9, characterized in that it's mixing the high molecular weight copolymer with the low molecular weight polyolefin and / or Dye includes. 14. Process for the preparation of a composition according to claim 9, which is the copolymerization of Monomers (a) and (b) in the presence of the lower molecular polyolefins and / or the dye and in the presence of the polyfunctional polymer insurance initiator. 15. Use of a composition according to one of Claims 1 to 9 as toner binder for electrophotographic toner. 16. A method for fixing a toner image with a melting roll, wherein the toner image a toner comprising the composition of one of claims 1 to 9 contains.